EP3106542B1 - Dispositif de synthèse de liaisons contenant de l'hydrogène - Google Patents

Dispositif de synthèse de liaisons contenant de l'hydrogène Download PDF

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Publication number
EP3106542B1
EP3106542B1 EP16172505.6A EP16172505A EP3106542B1 EP 3106542 B1 EP3106542 B1 EP 3106542B1 EP 16172505 A EP16172505 A EP 16172505A EP 3106542 B1 EP3106542 B1 EP 3106542B1
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EP
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Prior art keywords
tubular
electrochemical cells
hydrogen ions
tubular electrochemical
synthesis
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EP16172505.6A
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German (de)
English (en)
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EP3106542A1 (fr
Inventor
Stefan LUEDDECKENS
Wolfgang Lippmann
Sebastian Unger
Antonio Hurtado
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Technische Universitaet Dresden
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Technische Universitaet Dresden
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1516—Multisteps
    • C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C10G2/341—Apparatus, reactors with stationary catalyst bed
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/70—Assemblies comprising two or more cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • the invention relates to the fields of mechanical engineering and chemistry and relates to an apparatus for the synthesis of hydrogen-containing compounds, as can be used for example for the synthesis of methane, methanol alkanes, alkenes or other hydrocarbons.
  • the electrical energy conversion processes used to drive chemical reactions are also referred to as power-to-gas (PTG) or power-to-liquid (PTL) processes.
  • the synthesis gas required for the different types of synthesis consisting of hydrogen and carbon monoxide and / or carbon dioxide, is provided by electrochemical means by an electrolysis ( DE 10 2013 017 914 A1 ).
  • Carbon monoxide can be obtained not only by the electrolysis of carbon dioxide but also from the shift reaction, a reaction of hydrogen and carbon dioxide to water and carbon monoxide ( US 8540898 A1 ).
  • the synthetic reactions are also feasible with carbon dioxide, the conversions being significantly lower than with carbon monoxide. This requires a more complicated separation of product and unreacted starting materials.
  • the decision for a reaction with carbon dioxide or carbon monoxide depends on the one hand on the individual requirements of Hydrocarbon syntheses and on the other hand after weighting the simplest possible structure at low process temperatures or the highest possible efficiency.
  • electrolyzer a device is referred to, in which by means of electric current, a chemical reaction, ie a material conversion, is brought about: there is an electrolysis.
  • electrolysis a chemical reaction
  • Alkaline electrolysers are the only major industrial uses, but are generally less suitable for power-to-gas / liquid technologies due to comparable low efficiencies and the lack of recuperation by the waste heat generation at low temperature level Hochtemperaturelektrolyseure. For the latter, however, the long-term performance in commercial plants can not yet be proven.
  • a fuel cell is a galvanic cell that converts the chemical reaction energy of a continuously supplied fuel and an oxidant into electrical energy.
  • An electrochemical cell can be operated both as a fuel cell and as an electrolyzer by either applying a voltage or creating an electrochemical potential.
  • a cell that works in both directions is also known as a reversible fuel cell (RFC).
  • RFC reversible fuel cell
  • This mode of operation is particularly possible when the catalysts are equivalent in fuel cell and electrolysis operation, for example when nickel / ruthenium is used in the production of synthetic methane.
  • the advantage of an RFC is above all in the increase in full load hours and thus the economic utilization of the cell by electrolysis is operated at low electricity prices and electricity is generated at high electricity prices, for example, from natural gas or synthetic methane. With an RFC so the operation of an energy storage is possible ( US 8748052 A1 ).
  • Fuel cells and electrolyzers can also be distinguished by their operating temperatures and / or the electrolytes used. As low-temperature cells cells with a working temperature below 200 ° C, rather below 100 ° C, referred to, as are common in the use of alkali metal or polymer electrolytes. Above these temperatures, only molten carbonate cells are currently in use as fuel cells which use carbonates which are liquid at 500 ° C. as the electrolyte.
  • a well-known ceramic electrolyte is yttrium-stabilized zirconium oxide (YSZ), which conducts oxygen ions from 700 ° C. By special doping, but also by using other ceramics working temperatures between 400 and 700 ° C are possible at which these ceramics conduct protons.
  • YSZ yttrium-stabilized zirconium oxide
  • proton-conducting cells Another advantage of using proton-conducting cells is the presence of the desired product, the hydrogen, in very high purity. In the case of oxide-conducting cells, this is always contaminated with a residue of the educts, generally water. However, water inhibits the subsequent synthesis reactions and must be removed. When this happens by condensation, the heat of the hydrogen is lost, which would be needed in a subsequent shift reaction as an endothermic reaction.
  • the use of proton-conducting electrolytes in the electrolysis also causes the presence of hydrogen at the electrolyte interface in an initially atomic, nascent form, whereby this is particularly reactive.
  • the device according to the invention for the synthesis of hydrogen-containing compounds, consisting of at least one cladding tube.
  • This cladding tube is advantageously made of a metallic material, such as stainless steel.
  • a greater / higher pressure than the ambient pressure prevails in the cladding tube interior for the realization of the synthesis conditions at least in the working stage, which can be carried out in a simplified manner by the design of the functional components of the device in the form of tubes. All supplied or discharged media in the Hüllrohrinnenraum must therefore naturally under the pressure that prevails in the Hüllrohrinnenraum supplied and removed.
  • the cladding tube can in particular absorb pressures in the interior of 0.5 to 40 MPa.
  • a Hüllrohrinnenraum are at least one hydrogen ion conducting tubular electrochemical cell and at least one non-hydrogen ion conductive tubular electrochemical cell, or there are at least two cladding tubes in which in a Hüllrohrinnenraum at least one hydrogen ion conductive tubular electrochemical cell and in the other Hüllrohrinnenraum at least one non-hydrogen ion-conducting tubular electrochemical cell is present, wherein all cells are spaced from the inner wall of the cladding tube,
  • the hydrogen ion-conducting tubular electrochemical cell consists of a tubular solid electrolyte, in which a coating is arranged on at least the inner and outer walls, which consists of cathode or anode material.
  • the hydrogen ion-conducting tubular electrochemical cell advantageously has dimensions of 1 mm to 1000 mm internal diameter and 20 mm to 2000 mm in length.
  • the solid electrolyte of the hydrogen ion conductive tubular electrochemical cell there may be present ceria, beta-aluminate, calcium zirconate, sodium titanate or other titanates or zirconia with additives such as yttrium and barium.
  • the material for the solid electrolyte may be ceria, yttrium stabilized zirconia or scandium stabilized zirconia.
  • ceramic-metal composites of nickel-yttrium-stabilized zirconia, nickel alloys, platinum metals, or composites of oxide ceramics and these metals, and as the cathode material lanthanum strontium manganite, lanthanum strontium cobaltite ferrite, nickel alloys or platinum metals may be present at least the inner and outer sides of the tubular solid electrolyte are at least partially, advantageously completely, coated with the anode or cathode material.
  • the surfaces of the tubular solid electrolyte are at least on the cathode side made of a catalyst material and / or wholly or partially coated therewith, and / or at least partially the anode and / or cathode material is a catalyst material, and / or
  • the catalyst material is positioned on the cathode and / or anode material.
  • catalyst materials can be advantageously each platinum metals, nickel or iron compounds for hydrogen synthesis, and / or for the synthesis of oxygen, and / or nickel or ruthenium-containing materials for methane synthesis or copper-zinc oxide-alumina materials for methanol synthesis, or cobalt-containing catalysts generally for hydrocarbon synthesis.
  • the catalyst materials are only on the surface of the solid electrolyte and / or as anode and / or cathode material and / or on the surface of the anode and / or or cathode positioned.
  • the catalyst material may also be positioned on the surface of the solid electrolyte and / or as anode and / or cathode material and / or on the surface of the anode and / or cathode and / or or in the room around the cathode.
  • the cladding tube interior also has at least one heating element, which may be, for example, an electrical resistance heating element.
  • a heating element which may be, for example, an electrical resistance heating element. It may advantageously be summarized 2 to 1000 individual hydrogen ion-conducting tubular electrochemical cells or as a bundle of such cells in a cladding tube or within several cladding tubes. In the case of several cladding tubes, significantly more than 1000 individual hydrogen-ion-conducting tubular electrochemical cells can then also be present in the cladding tubes and / or combined in bundles. Also, several cladding tubes can be combined into modules and assembled in terms of their operation.
  • These individual or bundled cells and / or cladding tubes may have at least partial or complete common leads and at least partially or completely common drains and may also be connected to a common power supply and control mechanisms, and in the case of multiple hydrogen ion conducting tubular electrochemical cells, the tubes may or bundles over and / or behind each other in the Hüllrohrinnenraum be arranged.
  • the hydrogen-ion-conducting tubular electrochemical cells on the anode side of the cell there is a feed for water or steam and on the cathode side of the cell a feed for carbon dioxide or carbon monoxide or nitrogen.
  • the at least one hydrogen-ion conducting tubular electrochemical cell and the at least one non-hydrogen ion conducting tubular electrochemical cell are functionally connected in series and / or in parallel within a cladding tube or within different cladding tubes.
  • heat exchangers or heat exchangers for recuperation of waste heat exothermic processes that take place in the cladding, the waste heat from synthesis reaction, waste heat of the product stream, waste heat of the intermediates from the electrolysis and / or the shift reaction, and / or use compressor waste heat and / or it can
  • Separation devices such as devices for the separation of main and by-products, such as water and unreacted starting materials, for example by distillation, condensation or membrane processes, or for the separation of water vapor and / or there may be devices for the synthesis and / or processing of water, hydrogen , Carbon monoxide and / or carbon dioxide.
  • the feeds for water or water vapor on the anode side of a hydrogen ion conductive tubular electrochemical cell with the exits of heat exchangers or heat exchangers for recuperation of waste heat exothermic processes are functionally connected, and the feeds for carbon monoxide or on the cathode side of the hydrogen ion conductive tubular electrochemical Cells are operatively connected to the drains of an oxygen ion conducting tubular electrochemical cell, and the drains for oxygen on the anode side of a hydrogen ion conducting tubular electrochemical cell are operatively connected to the supply of an oxygen ion conducting tubular electrochemical cell.
  • the modular construction according to the invention results in particular from the fact that one or more hydrogen ion-conducting tubular electrochemical cells are arranged as a bundle in a cladding tube and that these can be arranged and operated together as modules to plants of any size. Also, individual hydrogen ion conducting tubular electrochemical cells and individual non-hydrogen ion conducting tubular electrochemical cells may be present in different cladding tubes and then combined into a bundle in parallel operation, or connected in series as modules. For a flexible arrangement of the device and a flexible process implementation is possible, which also leads to a high reliability and ease of maintenance of the entire system, especially since there is the possibility of individual controllability of the modules.
  • a plurality of tubular cells or bundles of tubular cells in a cladding tube wherein the individual cells may consist of different solid electrolyte, anode and / or cathode materials and thus process and process various substances such as water vapor or carbon dioxide or nitrogen can produce hydrogen-containing compounds of optimal composition.
  • further devices may be arranged inside the cladding tube, such as devices for the synthesis and / or processing of water, hydrogen, carbon monoxide and / or carbon dioxide or Nitrogen.
  • one or more further devices can be arranged outside of the cladding tube, which are directly connected to devices in the interior of the cladding tube, such as heat transfer devices or heat exchangers for recuperation of waste heat exothermic processes in the cladding tube, such as the waste heat of the synthesis reaction, the waste heat of the product stream, the waste heat of the intermediates from the electrolysis and / or the compressor waste heat, and / or separation devices, such as devices for the separation of water vapor or condensation of ammonia.
  • heat transfer devices or heat exchangers for recuperation of waste heat exothermic processes in the cladding tube such as the waste heat of the synthesis reaction, the waste heat of the product stream, the waste heat of the intermediates from the electrolysis and / or the compressor waste heat, and / or separation devices, such as devices for the separation of water vapor or condensation of ammonia.
  • the line of hydrogen ions either in the tube inside or on the tube outside of the hydrogen ion-conducting tubular electrochemical cell realized.
  • a catalyst material is present in each case or even only on one side, ie on the side of the cathode or the anode.
  • the catalyst material corresponds to conventional catalysts for the various hydrocarbon syntheses, such as nickel or ruthenium-containing catalysts for methane synthesis or copper-zinc oxide-alumina catalysts for the synthesis of methanol.
  • the operation of the device according to the invention is the following.
  • the hydrogen ion conductive tubular electrochemical cell positioned in the cladding tube interior has a supply of water vapor and an exhaust for oxygen on the anode side of the cell.
  • the hydrogen ions are conducted to the cathode side of the cell, on which hydrogen is then present.
  • the particular advantage of the present invention when using hydrogen ion-conducting electrochemical cells is that pure hydrogen is provided and no purification process is required.
  • On the cathode side of the hydrogen ion conducting tubular electrochemical cell is a feed for carbon monoxide and a discharge for hydrocarbons, and possibly unreacted reactants or other reaction products.
  • the reaction on the cathode side of the hydrogen ion conducting tubular electrochemical cell occurs between the generated hydrogen and the supplied carbon monoxide.
  • the reaction leads to the synthesis of hydrogen-containing compounds, such as on the one hand to hydrocarbons, such as methane, methanol, alkanes, alkenes, gasoline or diesel fuels.
  • the anode material can be arranged on the inside of the tubular solid electrolyte. Then advantageously in the tube interior of the cell water vapor on one side and on the other side oxygen discharged. The hydrogen then forms on the outside of the tubular solid electrolyte. Carbon monoxide is then added to the space around the outside of the tubular solid electrolyte and the resulting hydrogen-containing compounds and non-reactively reacted starting materials or other reaction products are removed.
  • the cathode material is arranged on the inside of the tubular solid electrolyte, the inlets and outlets of the materials mentioned are just the other way around, so carbon monoxide are added to the tube interior of the cell and discharged the resulting hydrogen-containing compounds and non-reactively reacted starting materials or other reaction products, and Water vapor is fed into the space around the outside of the tubular solid electrolyte on one side and oxygen on the other side.
  • At least one or more oxygen ion-conducting tubular electrochemical cells are present in the cladding tube.
  • the oxygen generated at the one or more hydrogen ion conductive tubular electrochemical cells may be directed to the anode side of the oxygen ion conductive tubular electrochemical cells.
  • carbon dioxide can be supplied, which reacts to carbon monoxide, which in turn can be introduced into the reaction space at the or the hydrogen ion-conducting tubular electrochemical cells via the feed.
  • the conduction of the oxygen ions can also take place either from inside to outside of the tubular solid electrolyte of the cell or from outside to inside.
  • a compression of the supplied water vapor to the existing pressure in the cladding tube can already, at least partially, be achieved by the evaporation of the necessary feed water, in which waste heat streams described above can be recuperated.
  • Another, for example Mechanical compression is dependent on the desired reaction product and the associated reaction conditions.
  • An evaporation and compression advantageously outside the cladding tube is realized by a heat transfer medium, with which the water vapor or water is separated and the energy thereby obtained can be transferred to the starting materials.
  • the heat transfer medium corresponds to the feedwater which is heated and vaporized at the various stations of heat transfer.
  • the use of a separate heat transfer medium depends on the pressure in the cladding tube. At high pressures, such as in the methanol synthesis (about 5 MPa), a complete evaporation of the water at this pressure level is not possible, so that the heat is transferred via a medium to the feed water, which may then initially be at lower pressure.
  • catalyst material it is also possible advantageously for catalyst material to be present that supports at least the electrolysis process, for example nickel or platinum metals.
  • the catalyst materials of the synthesis processes can be applied both directly to the electrodes in order to allow reactions directly at the interfaces, as well as in the cavity in various variants, for example as pellets, foam or wool.
  • the respective functional surfaces of the solid electrolyte can be structured, which can be realized for example with a laser treatment, ion irradiation or other processes.
  • educts are to be understood as meaning both the hydrogen synthesized by the cells and also carbon dioxide and / or carbon monoxide supplied.
  • further reaction products are to be understood as meaning, for example, water, with customary reactions taking place in the course of this reaction even small amounts of other than the desired substances can arise, which are predominantly themselves hydrocarbons.
  • the indirect heating of the cladding tube is particularly advantageous for the heat recovery and heating of the entire device from the outside, as well as the cooling of the synthesis reaction.
  • the heat transfer medium may simultaneously be the feed water for the electrolysis or a separate heat transfer circuit. This depends on the production of the desired end product and in particular on the temperature required for this, since it is advantageous to vaporize the feed water by the waste heat.
  • a heat recovery is usefully always sought according to the invention.
  • the use of the waste heat for the preheating and, if possible in the individual process management, the evaporation of the feedwater is the essential recovery stage.
  • the preheating of the carbon dioxide as far as it does not already have operating temperature by compression, can be carried out according to the invention.
  • carbon dioxide may be at a temperature above the optimum reaction temperature due to compression.
  • the carbon dioxide can be cooled in conjunction with a heat recovery.
  • the unreacted educts of the reactions contained in the product stream are dewatered and recycled, whereby a small proportion of this recyclate can be disposed of in order to prevent the accumulation of contaminants.
  • the recycled educts are also preheated by heat recovery.
  • Another heat source is the still warm product flow. Its heat is also used to preheat the starting materials and / or educts.
  • the intermediates from electrolysis and / or shift reaction may have a temperature above the temperature necessary for the subsequent reaction. By cooling these intermediates further heat can be recuperated.
  • Compressors can be used for increasing the pressure of the starting materials and / or reaction products and / or educts, for example, such as water and carbon dioxide.
  • water is already evaporated by recuperation at process pressure. This is especially true at Procedures requiring low process pressure, such as in methane synthesis, possible.
  • post-compaction may be used.
  • a particular advantage of the solution according to the invention consists in its modular construction in small, interchangeable modules.
  • several individual cells or multiple cells can be modularly interconnected as bundles in one or more cladding and the peripheral components, such as water and carbon dioxide compressor, steam storage, heat exchanger units and electrical components can be shared.
  • different process guides can be realized within the cladding tube or with different cladding tubes.
  • the modular design offers the further advantage that individual modules can be replaced in case of damage or failure and then the entire device can continue working.
  • tubular structure of the device according to the invention is an advantage, since rapid load changes are possible and the mechanical strength is significantly higher than in planar devices.
  • tubular cells with small inner diameters Through the use of tubular cells with small inner diameters, the previous disadvantage of tubular electrochemical cells in the form of the low conversion of the material flow in the center of the tubes can be eliminated.
  • the material flow can be better converted by internals or by partial radial inflow and turbulence of the material flow.
  • the turbulence also leads to a more reactive boundary layer.
  • a central stream can be prevented by installing a central body.
  • the combination of hydrogen ion-conducting water electrolysis and oxygen ion-conducting carbon dioxide electrolysis or the direct use of carbon dioxide for the synthesis of hydrocarbons can be carried out with minimal process outlay and at moderate temperatures.
  • electrolysis of at least hydrogen and also oxygen and furthermore the synthesis of hydrocarbon-containing compounds are for the first time accommodated compactly in a common cladding tube.
  • a 80 mm diameter stainless steel cladding contains a bundle of 53 tubular hydrogen electrochemical cells which conduct hydrogen ions.
  • the 53 hydrogen ion-conducting tubular electrochemical cells have a tubular solid electrolyte of barium-doped yttrium-stabilized zirconia, each having a length of 130 mm and an inner diameter of 1 mm.
  • a 1 mm thick layer of nickel foam is applied as the anode material with a 2 mg / cm 2 thick layer of platinum as the catalyst material.
  • a 1 mm thick layer of nickel foam is applied as the cathode material and a 2 mg / cm 2 thick layer of platinum as the catalyst material.
  • the cladding tube has a pressure of 1 MPa inside. All incoming and outgoing media are compressed outside the cladding tube to this pressure and then fed into the cladding tube.
  • the cladding tube has feedthroughs of electrical connections for the hydrogen ion-conducting electrochemical cells, as well as electrical heating elements in front of these cells.
  • From a steam storage steam is passed through the cladding tube in a manifold and thus in the hydrogen ion-conducting tubular electrochemical cells and converted to hydrogen and oxygen.
  • the oxygen is removed from the device and does not participate in any further process steps.
  • the hydrogen flows to the outside of the cells in the space between Hüllrohrinnenwandung and outside of the hydrogen ion conducting electrochemical cells. In this room also the supplied carbon dioxide is passed.
  • the hydrogen-carbon dioxide mixture is then converted here to methane and water, wherein the synthesis region is filled with a bed of nickel-aluminum oxide catalyst pellets.
  • the reaction is catalyzed by the catalyst material present on the outside of the electrochemical cells and by the catalyst material present in the space between the 53 hydrogen ion conducting tubular electrochemical cells.
  • the consisting of methane and water product stream, and unreacted hydrogen and carbon dioxide are removed from the cladding tube and separated by membrane processes. Unreacted hydrogen and carbon dioxide are returned to the cladding tube on the outside of the cells.
  • Feed water is compressed by a pump to the pressure prevailing in the interior of the cladding tube and heated by boiling product streams, unreacted starting materials and an electrical heating element outside the cladding tube to boiling temperature.
  • This heated to boiling temperature water is passed into the area around the cells where it absorbs the exothermic reaction energy from the reactions there from the reactions and thereby the water is evaporated.
  • the steam is fed to an external steam storage. This is, as well as the electrochemical cells electrically heated by resistance heaters and thus heats the water vapor on the for the Water electrolysis required temperature.
  • This water vapor is supplied to the cladding tube and the interior of the 53 hydrogen ion-conducting tubular electrochemical cells.
  • the supplied carbon dioxide is compressed by an electrically operated compressor to the pressure in the cladding tube. All devices outside the cladding tube are unique and can provide more cladding in a modular design.
  • the cladding tubes can also be operated in reverse order as a fuel cell, wherein methane is compressed instead of carbon dioxide.
  • Example 2 Methanol synthesis with hydrogen ion-conducting water electrolysis and oxygen ion-conducting carbon dioxide electrolysis
  • the 48 oxygen ion conductive tubular electrochemical cells comprise a tubular solid electrolyte of yttria-stabilized zirconia, each having a length of 130 mm and an inner diameter of 1 mm.
  • a 1 mm thick layer of nickel foam is applied as the anode material with a 2 mg / cm 2 thick layer of platinum as the catalyst material.
  • a 1 mm thick layer of nickel foam is applied as the cathode material and a 2 mg / cm 2 thick layer of platinum as the catalyst material. From the interior of the 48 oxygen ion-conducting tubular electrochemical cells, there are discharges for oxygen.
  • the cladding tube has feedthroughs of electrical connections for the electrochemical cells, as well as electrical heating elements in front of these cells.
  • From a steam storage steam is passed through the cladding tube in a manifold and thus in the hydrogen ion-conducting tubular electrochemical cells and converted to hydrogen and oxygen.
  • the oxygen is passed into the feed into the interior of the 48 oxygen-ion-conducting tubular electrochemical cells to be discharged together with oxygen therefrom.
  • the carbon dioxide supplied to the outside of the 48 oxygen ion conductive tubular electrochemical cells is reduced to carbon monoxide and oxygen.
  • the conversion is 80%, which is why a mixture with a carbon monoxide to carbon dioxide in the ratio of 4: 1 is present.
  • the oxygen from water and carbon dioxide electrolysis is removed from the device and does not participate in any further process steps.
  • the hydrogen flows into a space between Hüllrohrinnenwandung and outer wall of the hydrogen ion-conducting electrochemical cells and is fed to a heat exchanger and cooled to methanol synthesis temperature.
  • the mixture of carbon dioxide and carbon monoxide flows from the interior of the oxygen ion-conducting tubular electrochemical cells in a heat exchanger and there also cooled to methanol synthesis temperature.
  • the hydrogen and the mixed stream of carbon dioxide and carbon monoxide are fed in the downstream of the electrolysis reaction region and converted to methanol and water.
  • the reaction is catalyzed by the incorporated catalysts as a bed of copper-zinc oxide-aluminum oxide pellets.
  • the consisting of methanol and water product stream, and unreacted hydrogen, carbon monoxide and carbon dioxide are removed from the cladding tube and separated by condensation. Unreacted hydrogen, carbon monoxide and carbon dioxide are recycled to the reaction zone.
  • Feed water is compressed by a pump to the total prevailing in the cladding tube pressure of 10 MPa and by resulting product streams and unreacted starting materials in the Condensation cooling outside the cladding tube heated.
  • the feed water is further supplied to the cladding tube and further heated by flow around the region of the exothermic methanol reaction, and by cooling the electrolysis products in the heat exchangers.
  • the heated feed water is then fed to an external, electrically heated steam generator with steam storage. This is, as well as the electrochemical cells electrically heated by resistance heaters and generated and superheated steam to the temperature required for the electrolysis of water.
  • This water vapor is supplied to the cladding tube and the 53 hydrogen ion-conducting tubular electrochemical cells.
  • the supplied carbon dioxide is compressed by an electrically operated compressor to the prevailing pressure in the cladding tube. All devices outside the cladding tube are unique and can provide more cladding in a modular design.
  • a device according to Example 1 is used for ammonia synthesis.
  • the supplied substances are water and nitrogen (instead of carbon dioxide), which have been compressed to a pressure of 30 MPa, which also corresponds to the internal pipe pressure in the cladding tube.
  • the water is heated by a separate cooling water circuit, which flows around the synthesis area, after its compression and evaporated in an electrically heatable steam storage.
  • Hydrogen and nitrogen are present in the synthesis range in a ratio of 3: 1.
  • a bed of catalyst pellets from the usual for this synthesis materials based on magnetite with cobalt as a promoter is present.
  • the resulting ammonia is fed to a condenser where it transfers its heat to the feed water and then stored in liquid form.

Claims (12)

  1. Dispositif pour la synthèse de composés contenant de l'hydrogène,
    - constitué par au moins un tube de gainage, qui comprend dans l'espace intérieur du tube de gainage au moins une cellule électrochimique tubulaire conduisant les ions hydrogène et au moins une cellule électrochimique tubulaire conduisant des ions non-hydrogène, qui sont chacune agencées espacées de la paroi intérieure du tube de gainage, la cellule électrochimique tubulaire conduisant les ions hydrogène étant constituée par un électrolyte solide tubulaire, et un revêtement étant agencé au moins sur la paroi intérieure et extérieure de l'électrolyte solide tubulaire, qui est constitué par un matériau de cathode ou d'anode,
    - ou constitué par au moins deux tubes de gainage, dans l'espace intérieur de tube de gainage d'un desquels est présente au moins une cellule électrochimique tubulaire conduisant les ions hydrogène et dans l'autre espace intérieur de tube de gainage est présente au moins une cellule électrochimique conduisant des ions non-hydrogène, les deux cellules étant chacune agencées espacées de la paroi intérieure du tube de gainage, et la cellule électrochimique tubulaire conduisant les ions hydrogène étant constituée par un électrolyte solide tubulaire, et un revêtement étant agencé au moins sur la paroi intérieure et extérieure de l'électrolyte solide tubulaire, qui est constitué par un matériau de cathode ou d'anode,
    - une pression supérieure à la pression ambiante étant présente dans l'espace intérieur de tube de gainage de chaque tube de gainage au moins au stade de travail,
    - et un élément chauffant étant présent dans l'espace intérieur de tube de gainage d'au moins un tube de gainage,
    - et, au moins dans les cellules électrochimiques tubulaires conduisant les ions hydrogène, les surfaces de l'électrolyte solide tubulaire comprenant un matériau catalytique au moins sur le côté de la cathode et étant revêtues en totalité ou en partie avec celui-ci, et/ou le matériau d'anode et de cathode étant au moins en partie un matériau catalytique, et le matériau catalytique étant positionné sur le matériau de cathode et/ou d'anode,
    - et, au moins dans les cellules électrochimiques tubulaires conduisant les ions hydrogène, une alimentation pour de l'eau ou de la vapeur d'eau étant présente sur le côté de l'anode de la cellule, et une alimentation pour du monoxyde de carbone étant présente sur le côté de la cathode de la cellule,
    - et, au moins dans les cellules électrochimiques tubulaires conduisant les ions hydrogène, une sortie pour de l'oxygène étant présente sur le côté de l'anode, et une sortie pour des hydrocarbures sur le côté de la cathode,
    - et des cellules électrochimiques tubulaires conduisant les ions oxygène étant présentes en tant que cellules électrochimiques tubulaires conduisant des ions non-hydrogène ; dans les cellules électrochimiques tubulaires conduisant les ions oxygène, une alimentation pour du dioxyde de carbone et une sortie pour du monoxyde de carbone étant présentes sur le côté de la cathode,
    - et ladite au moins une cellule électrochimique tubulaire conduisant les ions hydrogène et ladite au moins une cellule électrochimique tubulaire conduisant des ions non-hydrogène étant raccordées fonctionnellement en série et/ou en parallèle dans un tube de gainage ou dans différents tubes de gainage.
  2. Dispositif selon la revendication 1, dans lequel 2 à 1 000 cellules électrochimiques tubulaires conduisant les ions hydrogène sont rassemblées sous la forme d'un faisceau dans un tube de gainage ou dans plusieurs tubes de gainage, et/ou dans lequel plusieurs cellules électrochimiques tubulaires conduisant les ions hydrogène sont agencées sous la forme de tubes ou de faisceaux les unes sur les autres et/ou les unes après les autres dans un espace intérieur de tube de gainage.
  3. Dispositif selon la revendication 1, dans lequel des cellules électrochimiques tubulaires conduisant les ions oxygène sont présentes en tant que cellules électrochimiques tubulaires conduisant des ions non-hydrogène, et des dispositifs de transfert de chaleur ou des échangeurs de chaleur sont en outre présents pour la récupération de la chaleur résiduaire de procédés exothermiques dans les tubes de gainage, telle que la chaleur résiduaire de la réaction de synthèse, la chaleur résiduaire du courant de produits, la chaleur résiduaire des produits intermédiaires de l'électrolyse et/ou de la réaction de conversion et/ou la chaleur résiduaire du compresseur, et/ou des dispositifs de séparation, tels que des dispositifs pour la séparation de produits principaux et secondaires, tels que l'eau et les réactifs non réagis, par exemple par distillation, condensation ou des procédés sur membrane, ou pour la séparation de vapeur d'eau, et/ou des dispositifs pour la synthèse et/ou pour le traitement d'eau, d'hydrogène, de monoxyde de carbone et/ou de dioxyde de carbone.
  4. Dispositif selon la revendication 2 ou 3, dans lequel une ou plusieurs cellules électrochimiques tubulaires conduisant les ions oxygène sont présentes dans un tube de gainage avec une plusieurs cellules électrochimiques tubulaires conduisant les ions hydrogène ou dans plusieurs tubes de gainage.
  5. Dispositif selon la revendication 1, dans lequel le tube de gainage est constitué par un matériau métallique, avantageusement pour l'absorption de pressions dans l'espace intérieur du tube de gainage de 0,1 à 40 MPa.
  6. Dispositif selon la revendication 1, dans lequel ladite au moins une cellule électrochimique tubulaire conduisant les ions hydrogène présente des dimensions de 1 mm à 1 000 mm de diamètre intérieur et de 20 mm à 2 000 mm de longueur.
  7. Dispositif selon la revendication 1, dans lequel les cellules électrochimiques comprennent en tant que matériau d'anode un composite céramique-métal (Cermet) à base d'oxyde de zirconium stabilisé par du nickel-yttrium, des alliages de nickel, des métaux du groupe du platine ou des composites de céramiques oxydées et de ces métaux, et en tant que matériau de cathode de la manganite de lanthane-strontium, de la cobaltite-ferrite de lanthane-strontium, des alliages de nickel ou des métaux du groupe du platine, au moins les côtés intérieurs et extérieurs de l'électrolyte solide tubulaire étant revêtus au moins en partie, avantageusement en totalité.
  8. Dispositif selon la revendication 1, dans lequel un matériau catalytique est présent dans les cellules électrochimiques, des métaux du groupe du platine, des composés de nickel et de fer pour la synthèse d'hydrogène et/ou pour la synthèse d'oxygène, et/ou des matériaux contenant du nickel ou du ruthénium pour la synthèse de méthane ou des matériaux à base de cuivre-oxyde de zinc-oxyde d'aluminium pour la synthèse de méthanol, ou des catalyseurs contenant du cobalt en général pour la synthèse d'hydrocarbures étant respectivement présents en tant matériaux catalytiques.
  9. Dispositif selon la revendication 1, dans lequel un ou plusieurs éléments chauffants résistifs électriques sont présents en tant qu'élément chauffant.
  10. Dispositif selon la revendication 1, dans lequel certaines ou toutes les cellules électrochimiques tubulaires conduisant les ions hydrogène et certaines ou toutes les cellules électrochimiques tubulaires conduisant des ions non-hydrogène sont raccordées fonctionnellement en parallèle et comprennent des alimentations et des sorties séparées pour les produits de départ et finaux de chaque cellule.
  11. Dispositif selon la revendication 1, dans lequel certaines ou toutes les cellules électrochimiques tubulaires conduisant les ions hydrogène et certaines ou toutes les cellules électrochimiques tubulaires conduisant des ions non-hydrogène sont raccordées fonctionnellement en série, et les alimentations sont simultanément les sorties ou les sorties sont simultanément les alimentations d'autres cellules.
  12. Utilisation du dispositif selon la revendication 1, dans laquelle au moins de l'hydrogène est synthétisé, qui est utilisé dans le tube de gainage pour la synthèse d'hydrocarbures, tels que du méthane, des alcanes, des alcènes, des carburants automobiles ou diesel.
EP16172505.6A 2015-06-19 2016-06-01 Dispositif de synthèse de liaisons contenant de l'hydrogène Active EP3106542B1 (fr)

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DE102016213360A1 (de) * 2016-07-21 2018-01-25 Thyssenkrupp Ag Verfahren zur elektrochemischen Herstellung von Ammoniak
DE102020006326A1 (de) * 2020-10-15 2022-04-21 Wolfgang Winkler Integrierter Gaserzeuger und Stromspeicher

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AT368749B (de) * 1981-02-25 1982-11-10 Bbc Brown Boveri & Cie Verfahren zur kontinuierlichen herstellung von stickoxyd (no) und vorrichtung zur durchfuehrung des verfahrens
EP0497226B1 (fr) * 1991-01-29 1999-08-25 Mitsubishi Jukogyo Kabushiki Kaisha Méthode pour la production du méthanol utilisant chaleur et energie d'origine nucléaire
GB0210075D0 (en) * 2002-05-02 2002-06-12 Adelan Ltd Hydrogen generator
GB0602406D0 (en) 2006-02-07 2006-03-15 Univ St Andrews Reversible fuel cell
US20100086824A1 (en) * 2008-09-03 2010-04-08 Michael Homel Assemblies of hollow electrode electrochemical devices
EP2505261A4 (fr) 2009-11-27 2013-05-15 Murata Manufacturing Co Catalyseur de réaction anti-conversion catalytique, et procédé de production de gaz synthétique utilisant ce catalyseur
EP2528151A1 (fr) 2011-05-23 2012-11-28 The European Union, represented by the European Commission Pile à combustible à oxyde solide microtubulaire
DE102013017914A1 (de) 2012-10-21 2014-06-12 Karsten Lege Nutzung des "Power to Gas" Prinzips zur Anbindung von Offshore-Windparks
CN103103556B (zh) * 2013-03-06 2015-05-20 景德镇陶瓷学院 一种管式陶瓷膜反应器及其合成甲醇的方法

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